JP5051354B2 - Metal surface treatment agent, metal surface treated steel and method for treating the same, painted steel and method for producing the same - Google Patents

Description

  The present invention includes cold rolled steel, hot rolled steel, stainless steel, electrogalvanized steel, hot dip galvanized steel, zinc-aluminum alloy plated steel, zinc-iron alloy plated steel, zinc-magnesium alloy plated steel, For coated steel materials such as zinc-aluminum-magnesium alloy plated steel, aluminum-based plated steel, aluminum-silicon alloy-plated steel, tin-based plated steel, lead-tin alloy-plated steel, chromium-based plated steel, nickel-based plated steel The present invention relates to a metal surface treatment agent, a surface-treated steel material surface-treated with the treatment agent and a surface treatment method thereof, a coated steel material having an upper layer coating thereon, and a method for producing the same.

  Conventionally, chromium surface treatment agents such as chromate treatment and phosphoric acid chromate treatment have been applied to metal surface treatment agents, and they are still widely used today. However, according to recent trends in environmental regulations, the use of chromium may be limited in the future due to the toxicity of chromium, particularly carcinogenicity. Therefore, it has been desired to develop a metal surface treatment agent that does not contain chromium and has the same adhesion and corrosion resistance as the chromate treatment agent.

  Japanese Patent Application Laid-Open No. 11-29724 (Patent Document 1) proposes a non-chromium antirust treatment agent containing a thiocarbonyl group-containing compound, a phosphate ion, and further water-dispersible silica in an aqueous resin. However, although this system is excellent in corrosion resistance, workability and adhesion to the substrate are not sufficient. On the other hand, as for the silane coupling agent, an acidic surface treatment agent containing two types of silane coupling agents is disclosed in JP-A-8-73775 (Patent Document 2). However, this system lacks corrosion resistance for the purpose of requiring high corrosion resistance and workability after treating the metal surface.

  In relation to these, JP 2001-316845 A (Patent Document 3) discloses a non-chromate metal surface treatment agent containing a silane coupling agent, water-dispersible silica, zirconium or titanium ion as an essential component. Although the corrosion resistance and workability are improved, it cannot be said that the coating property to the base material and the adhesion strength with the upper layer film are sufficient.

  Moreover, in JP-A-10-60315 (Patent Document 4), a surface treatment agent for steel structures containing a silane coupling agent having a specific functional group that reacts with an aqueous emulsion is disclosed. The required corrosion resistance is only for a relatively mild test such as a wet test, and is not comparable in terms of corrosion resistance with a rust inhibitor that can withstand severe corrosion resistance such as the present invention.

  In view of the above, it has been desired to develop a metal surface treatment agent that can exhibit various properties such as corrosion resistance, work adhesion, coating property, and adhesive strength in a thin film.

JP-A-11-29724 JP-A-8-73775 JP 2001-316845 A Japanese Patent Laid-Open No. 10-60315

  The present invention has been made in view of the above circumstances, and is most suitable for metals, particularly metal-coated steel materials, does not contain chromium, and provides excellent workability, adhesion, and corrosion resistance as a pretreatment for coatings such as paints. An object of the present invention is to provide a non-chromate metal surface treatment agent that can be treated, a surface-treated steel material surface-treated with the treatment agent, a surface treatment method thereof, a coated steel material having an upper film thereon, and a method for producing the same. .

  As a result of intensive studies to achieve the above object, the present inventors have found that a reactive silyl group having a plurality of amino groups effective for the development of corrosion resistance and strongly bonding to the surface of the metal to be coated by a metasiloxane bond. By making an organic polymer having a group an essential component of a rust preventive agent, it is found that a metal surface treatment agent that is chromium-free and excellent in corrosion resistance, work adhesion, coating property, and adhesive strength can be obtained. It came to make this invention.

（式中、ｍは１０≦ｍ≦２６０、ｎは１≦ｎ≦１００であり、０．００３≦ｎ／（ｍ＋ｎ）≦０．９であり、Ｒ¹は水素原子、炭素数１〜４のアルキル基、又はアセチル基であり、ａ及びｂは１〜３の整数であり、Ｘは置換基を有してもよい炭素数１〜１０のアルキレン基であり、置換基は炭素数１〜６のアルキル基であり、Ｙは直接結合、酸素原子又はＣＨＲ⁵基を表し、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は水素原子又は炭素数１〜６のアルキル基を表すが、Ｒ³又はＲ⁴とＲ⁵が結合して飽和炭素環を形成してもよい。）
で表される繰り返し単位を有する、複数の１級アミノ基と加水分解性シリル基及び／又はシラノール基とを有する含ケイ素水溶性高分子化合物、下記一般式（２）

（式中、ｍは１０≦ｍ≦２６０、ｎは１≦ｎ≦１００であり、０．００３≦ｎ／（ｍ＋ｎ）≦０．９であり、Ｘは置換基を有してもよい炭素数１〜１０のアルキレン基であり、置換基は炭素数１〜６のアルキル基であり、Ｒ¹は水素原子、炭素数１〜４のアルキル基、又はアセチル基であり、Ｒ’は水素原子又はメチル基であり、ａは１〜３の整数である。）
で表される繰り返し単位を有する、複数の１級アミノ基と加水分解性シリル基及び／又はシラノール基とを有する含ケイ素水溶性高分子化合物、及び下記一般式（３）

（式中、ｍは１０≦ｍ≦２６０、ｎは１≦ｎ≦１００であり、０．００３≦ｎ／（ｍ＋ｎ）≦０．９であり、Ｘは置換基を有してもよい炭素数１〜１０のアルキレン基であり、置換基は炭素数１〜６のアルキル基であり、Ｒ¹は水素原子、炭素数１〜４のアルキル基、又はアセチル基であり、ａは１〜３の整数である。）
で表される繰り返し単位を有する、複数の１級アミノ基と加水分解性シリル基及び／又はシラノール基とを有する含ケイ素水溶性高分子化合物
からなる群より選択される重量平均分子量が３００〜３０００である化合物及び／又はその（部分）加水分解縮合物の１種又は２種以上を金属表面処理剤中に０．０１〜２００ｇ／Ｌ含まれるように水及び／又は有機溶媒に溶解してなり、更に、金属表面処理剤中に、水分散性シリカを固形分で０．０５〜１００ｇ／Ｌ含むことを特徴とする金属表面処理剤。
〔２〕 更に、金属表面処理剤中に、ジルコニウム化合物をジルコニウムイオンとして０．０１〜５０ｇ／Ｌ及び／又はチタニウム化合物をチタニウムイオンとして０．０１〜５０ｇ／Ｌ含むことを特徴とする〔１〕記載の金属表面処理剤。
〔３〕 更に、金属表面処理剤中に、チオカルボニル基含有化合物を０．０１〜１００ｇ／Ｌ及び／又は水溶性アクリル樹脂を０．１〜１００ｇ／Ｌ含むことを特徴とする〔１〕又は〔２〕記載の金属表面処理剤。
〔４〕 更に、金属表面処理剤中に、リン酸イオンを０．０１〜１００ｇ／Ｌ含むことを特徴とする〔１〕〜〔３〕のいずれかに記載の金属表面処理剤。
〔５〕 〔１〕〜〔４〕のいずれかに記載の金属表面処理剤で表面処理することを特徴とする鋼材の金属表面処理方法。
〔６〕 鋼材が金属被覆鋼材である〔５〕記載の金属表面処理方法。
〔７〕 〔５〕又は〔６〕記載の方法で得られる表面処理鋼材。
〔８〕 〔１〕〜〔４〕のいずれかに記載の金属表面処理剤で鋼材を処理した後、更に上層被膜層を設けることを特徴とする塗装鋼材の製造方法。
〔９〕 鋼材が金属被覆鋼材である〔８〕記載の塗装鋼材の製造方法。
〔１０〕 〔８〕又は〔９〕に記載の方法で得られる塗装鋼材。 That is, the present invention provides the following metal surface treatment agent, metal surface-treated steel material and method for treating it, and coated steel material and method for producing the same.
[1] under following general formula (1)

(In the formula, m is 10 ≦ m ≦ 260, n is 1 ≦ n ≦ 100, 0.003 ≦ n / (m + n) ≦ 0.9, and R ¹ is a hydrogen atom having 1 to 4 carbon atoms. An alkyl group or an acetyl group, a and b are integers of 1 to 3, X is an optionally substituted alkylene group having 1 to 10 carbon atoms, and the substituent is 1 to 6 carbon atoms. an alkyl group, Y is a direct bond, an oxygen atom or a CHR ⁵ group, represents an R ^2, R ^3, R ⁴ and R ⁵ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ³ or R ⁴ and R ⁵ may combine to form a saturated carbocycle.)
A silicon-containing water-soluble polymer compound having a plurality of primary amino groups and hydrolyzable silyl groups and / or silanol groups, having a repeating unit represented by the following general formula (2)

(In the formula, m is 10 ≦ m ≦ 260, n is 1 ≦ n ≦ 100, 0.003 ≦ n / (m + n) ≦ 0.9, and X is the carbon number that may have a substituent. 1 to 10 alkylene group, the substituent is an alkyl group having 1 to 6 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group, and R ′ is a hydrogen atom or A methyl group, and a is an integer of 1 to 3.)
A silicon-containing water-soluble polymer compound having a plurality of primary amino groups and a hydrolyzable silyl group and / or silanol group, and the following general formula (3):

(In the formula, m is 10 ≦ m ≦ 260, n is 1 ≦ n ≦ 100, 0.003 ≦ n / (m + n) ≦ 0.9, and X is the carbon number that may have a substituent. 1 to 10 alkylene group, the substituent is an alkyl group having 1 to 6 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group, and a is 1 to 3 (It is an integer.)
The weight average molecular weight selected from the group consisting of silicon-containing water-soluble polymer compounds having a plurality of primary amino groups and hydrolyzable silyl groups and / or silanol groups, having a repeating unit represented by the formula: And / or (part) hydrolysis condensate thereof is dissolved in water and / or an organic solvent so that the metal surface treatment agent contains 0.01 to 200 g / L. further, in the metal surface treatment agent, characterized and to Rukin genus surface treatment agent in that it comprises 0.05 to 100 g / L of water-dispersible silica solids.
[ 2 ] Further, the metal surface treatment agent contains 0.01 to 50 g / L of zirconium compound as zirconium ions and / or 0.01 to 50 g / L of titanium compound as titanium ions [1] The metal surface treating agent as described.
[ 3 ] The metal surface treatment agent further includes 0.01 to 100 g / L of a thiocarbonyl group-containing compound and / or 0.1 to 100 g / L of a water-soluble acrylic resin [1] or [2] The metal surface treatment agent according to [2] .
[ 4 ] The metal surface treatment agent according to any one of [1] to [ 3 ], further comprising 0.01 to 100 g / L of phosphate ions in the metal surface treatment agent.
[ 5 ] A metal surface treatment method for steel, characterized in that the surface treatment is performed with the metal surface treatment agent according to any one of [1] to [ 4 ].
[ 6 ] The metal surface treatment method according to [ 5 ], wherein the steel material is a metal-coated steel material.
[ 7 ] A surface-treated steel material obtained by the method according to [ 5 ] or [ 6 ].
[ 8 ] A method for producing a coated steel material, characterized by further providing an upper coating layer after treating the steel material with the metal surface treatment agent according to any one of [1] to [ 4 ].
[ 9 ] The method for producing a coated steel material according to [ 8 ], wherein the steel material is a metal-coated steel material.
[ 10 ] A coated steel material obtained by the method according to [ 8 ] or [ 9 ].

  The metal surface treating agent of the present invention is an organic polymer having a plurality of amino groups effective for the development of corrosion resistance and a reactive group that strongly binds to the surface of the metal to be coated, represented by a reactive silyl group. By using a polymer compound having a basic skeleton as an essential component, corrosion resistance, work adhesion, and adhesive strength are expressed by one component, and further, since it has a polymer unit, it is excellent in coating property.

Hereinafter, the present invention will be specifically described.
The metal surface treating agent of the present invention contains, as an essential component, a compound containing all of the following structures (a) to (c) in one molecule and / or (partial) hydrolysis condensate thereof, And / or dissolved in an organic solvent.
(A) A linear and / or branched organic polymer skeleton formed of carbon-carbon bonds and into which nitrogen atoms may be inserted.
(B) a primary, secondary or tertiary amino group.
(C) A silyl group having a hydrolyzable group and / or a hydroxyl group bonded by a silicon-carbon bond.

  The structure (a) is preferably a polymethylene polymer skeleton having 20 to 800 carbon atoms or a polyethyleneimine skeleton having 20 to 800 carbon atoms.

Moreover, as said (c) structure, it is preferable that it is a hydrolysable silyl group shown by a following formula.
-SiR _x Z _3-x
(In the formula, R is an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group; Is a halogen atom such as a chlorine atom, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group or the like, or an acetoxy group. x is an integer of 0-2.)

  As a compound containing the structure of said (a)-(c) suitable for using by this invention, several primary amino group which has a repeating unit represented by the following general formula (1)-(6) And one or more compounds selected from the group consisting of silicon-containing water-soluble polymer compounds having a hydrolyzable silyl group and / or silanol group.

（式中、ｍは１０≦ｍ≦２６０、ｎは１≦ｎ≦１００であり、Ｒ¹は水素原子、炭素数１〜４のアルキル基、又はアセチル基であり、ａ及びｂは１〜３の整数であり、Ｘは置換基を有してもよい炭素数１〜１０のアルキレン基であり、置換基は炭素数１〜６のアルキル基であり、Ｙは直接結合、酸素原子又はＣＨＲ⁵基を表し、Ｒ²，Ｒ³，Ｒ⁴及びＲ⁵は水素原子又は炭素数１〜６のアルキル基を表すが、Ｒ³又はＲ⁴とＲ⁵が結合して飽和炭素環を形成してもよい。）

(In the formula, m is 10 ≦ m ≦ 260, n is 1 ≦ n ≦ 100, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group, and a and b are 1 to 3) X is an optionally substituted alkylene group having 1 to 10 carbon atoms, the substituent is an alkyl group having 1 to 6 carbon atoms, and Y is a direct bond, an oxygen atom or CHR ^5. R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, but R ³ or R ⁴ and R ⁵ are combined to form a saturated carbocyclic ring. May be good.)

（式中、ｍは１０≦ｍ≦２６０、ｎは１≦ｎ≦１００であり、Ｘは置換基を有してもよい炭素数１〜１０のアルキレン基であり、置換基は炭素数１〜６のアルキル基であり、Ｒ¹は水素原子、炭素数１〜４のアルキル基、又はアセチル基であり、Ｒ’は水素原子又はメチル基であり、ａは１〜３の整数である。）

(In the formula, m is 10 ≦ m ≦ 260, n is 1 ≦ n ≦ 100, X is an alkylene group having 1 to 10 carbon atoms which may have a substituent, and the substituent is 1 to carbon atoms. 6 is an alkyl group, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group, R ′ is a hydrogen atom or a methyl group, and a is an integer of 1 to 3).

（式中、ｍは１０≦ｍ≦２６０、ｎは１≦ｎ≦１００であり、Ｘは置換基を有してもよい炭素数１〜１０のアルキレン基であり、置換基は炭素数１〜６のアルキル基であり、Ｒ¹は水素原子、炭素数１〜４のアルキル基、又はアセチル基であり、ａは１〜３の整数である。）

(In the formula, m is 10 ≦ m ≦ 260, n is 1 ≦ n ≦ 100, X is an alkylene group having 1 to 10 carbon atoms which may have a substituent, and the substituent is 1 to carbon atoms. 6 is an alkyl group, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group, and a is an integer of 1 to 3).

（式中、ｐは１０≦ｐ≦２００、ｑは１≦ｑ≦２００、ｒは１≦ｒ≦１００であり、Ｒ¹は水素原子、炭素数１〜４のアルキル基、又はアセチル基であり、ａ及びｂは１〜３の整数であり、Ｘは置換基を有してもよい炭素数１〜１０のアルキレン基であり、置換基は炭素数１〜６のアルキル基であり、Ｙは直接結合、酸素原子又はＣＨＲ⁵基を表し、Ｒ²，Ｒ³，Ｒ⁴及びＲ⁵は水素原子又は炭素数１〜６のアルキル基を表すが、Ｒ³又はＲ⁴とＲ⁵が結合して飽和炭素環を形成してもよい。）

(Wherein p is 10 ≦ p ≦ 200, q is 1 ≦ q ≦ 200, r is 1 ≦ r ≦ 100, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group. , A and b are integers of 1 to 3, X is an alkylene group having 1 to 10 carbon atoms which may have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, and Y is a direct bond, an oxygen atom or a CHR ⁵ group, R ^2, R ^3, R ⁴ and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ³ or R ⁴ and R ⁵ are bonded To form a saturated carbocyclic ring.)

（式中、ｐは１０≦ｐ≦２００、ｑは１≦ｑ≦２００、ｒは１≦ｒ≦１００であり、Ｘは置換基を有してもよい炭素数１〜１０のアルキレン基であり、置換基は炭素数１〜６のアルキル基であり、Ｒ¹は水素原子、炭素数１〜４のアルキル基、又はアセチル基であり、Ｒ’は水素原子又はメチル基であり、ａは１〜３の整数である。）

(Wherein p is 10 ≦ p ≦ 200, q is 1 ≦ q ≦ 200, r is 1 ≦ r ≦ 100, and X is an alkylene group having 1 to 10 carbon atoms which may have a substituent. The substituent is an alkyl group having 1 to 6 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group, R ′ is a hydrogen atom or a methyl group, and a is 1 It is an integer of ~ 3.)

（式中、ｐは１０≦ｐ≦２００、ｑは１≦ｑ≦２００、ｒは１≦ｒ≦１００であり、Ｘは置換基を有してもよい炭素数１〜１０のアルキレン基であり、置換基は炭素数１〜６のアルキル基であり、Ｒ¹は水素原子、炭素数１〜４のアルキル基、又はアセチル基であり、ａは１〜３の整数である。）

(Wherein p is 10 ≦ p ≦ 200, q is 1 ≦ q ≦ 200, r is 1 ≦ r ≦ 100, and X is an alkylene group having 1 to 10 carbon atoms which may have a substituent. The substituent is an alkyl group having 1 to 6 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group, and a is an integer of 1 to 3).

In the above formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and i-propyl. Group, n-butyl group, i-butyl group, t-butyl group and the like.
X is an alkylene group having 1 to 10 carbon atoms, such as a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, etc., which may have a substituent. The group is a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, pentyl group, i-pentyl group, hexyl group, etc. 6 alkyl groups.
Y represents a direct bond, an oxygen atom or a CHR ⁵ group, and R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group. Represents an alkyl group having 1 to 6 carbon atoms such as i-butyl group, t-butyl group, pentyl group, i-pentyl group, and hexyl group, but R ³ or R ⁴ and R ⁵ are bonded to each other. A saturated carbocyclic ring having 3 to 7 carbon atoms may be formed together with (CH ₂ ) _b and (when R ³ and R ⁵ are bonded together, further CR ⁴ OH).
a and b are integers of 1 to 3.
In addition, in the high molecular compound of said formula (1)-(6), the terminal is a hydrogen atom.

  In the above formulas (1) to (3), m and n are 10 ≦ m ≦ 260, 1 ≦ n ≦ 100, preferably 10 ≦ m ≦ 100, 1 ≦ n ≦ 80, and more preferably. 10 ≦ m ≦ 75 and 1 ≦ n ≦ 50. When 260 <m or 100 <n, the molecular weight is large, and the viscosity becomes very high at the stage of compound synthesis, so that stable production may not be possible. In addition, when m <10, particularly when m = 0, there is a possibility that sufficient water solubility cannot be obtained. Further, when n <1, there is a possibility that the adhesion with the inorganic material is insufficient.

  In the above formulas (1) to (3), m and n respectively represent the number of allylamine units in the molecule and the units in which allylamine and silane have reacted, and the ratio of m and n is the primary amino in the molecule. The ratio of groups to silyl groups is shown. In the present invention, the silane coupling agent reacted with the base resin polyallylamine in each case is an amount of the silyl group introduced (m) and the amount of the remaining amino group (n). The ratio is preferably 0.003 ≦ n / (m + n) ≦ 0.9, more preferably 0.06 ≦ n / (m + n) ≦ 0.5. When the ratio is smaller than this range, the adhesion with the metal steel material may be insufficient, and when the ratio is large, the solubility may be insufficient, and thus it may be difficult to produce the metal surface treatment agent.

  In the case of the above formulas (4) to (6), p, q, r are 10 ≦ p ≦ 200, 1 ≦ q ≦ 200, 1 ≦ r ≦ 100, preferably 10 ≦ p ≦ 100, 10 ≦ q ≦ 100 and 1 ≦ r ≦ 80, more preferably 10 ≦ p ≦ 75, 10 ≦ q ≦ 75, and 1 ≦ r ≦ 50. In the case of 200 <p or 100 <r, the molecular weight is large, and the viscosity becomes very high at the stage of compound synthesis, so that stable production may not be possible. Moreover, when p <10, particularly when p = 0, there is a possibility that sufficient water solubility cannot be obtained. If q <1, the water solubility may be insufficient and the adhesion with the substrate may be insufficient. Further, when r <1, there is a possibility that the adhesion with the inorganic material is insufficient.

  In the above formulas (4) to (6), p, q, and r respectively represent the number of ethyleneimine units in the molecule and the units in which ethyleneimine and silane have reacted, and the ratio of p and r is in the molecule. The ratio of secondary amino group and silyl group is shown. In the present invention, the above compound is prepared by reacting the silane coupling agent reacted with polyethyleneimine as the base resin in any case, the amount of silyl groups introduced (r) and the amount of residual secondary amino groups (p ) Ratio of 0.003 ≦ r / (p + r) ≦ 0.9, and more preferably 0.06 ≦ r / (p + r) ≦ 0.5. When the ratio is smaller than this range, the adhesion with the metal steel material may be insufficient, and when the ratio is large, the solubility may be insufficient, and thus it may be difficult to produce the metal surface treatment agent.

  In this invention, it is preferable that the weight average molecular weights of the said compound are 300-3000, More preferably, it is 1000-2000. When the molecular weight exceeds 3000, the compound is easily gelled, and it may be difficult to produce and store the treatment agent. On the other hand, when the molecular weight is less than 300, the polymerization cannot be controlled, and it may be difficult to synthesize the polymer itself. In addition, in this invention, this weight average molecular weight is a polystyrene conversion value by gel permeation chromatography (GPC) (hereinafter the same).

  In the present invention, the compound is dissolved in water and / or an organic solvent, and the metal surface treatment agent has a liquid form, but the concentration of the compound in the metal surface treatment agent is 0.000 in 1 liter of the metal surface treatment agent. It is preferably contained at a concentration of 01 to 200 g (hereinafter referred to as 0.01 to 200 g / L), preferably 0.05 to 100 g / L. If the content of the above compound is less than 0.01 g / L, the effect of improving the corrosion resistance, adhesion to the primer, adhesive strength, coating property, etc. may be reduced. May become saturated and uneconomical.

  Examples of the remaining component include water and / or an organic solvent that dissolves the compound. Examples of the organic solvent include alcohols such as methanol and ethanol, and amides such as formamide and N, N-dimethylformamide. Solvents are preferred, and methanol and ethanol are particularly preferred, but are not limited to those listed here.

  The metal surface treatment agent of the present invention may contain water-dispersible silica as an additional component. The water-dispersible silica is not particularly limited, but is preferably spherical silica, chain silica, or aluminum-modified silica that has few impurities such as sodium and is weakly alkaline. Examples of spherical silica include colloidal silica such as “Snowtex N” and “Snowtex UP” (both manufactured by Nissan Chemical Industries) and fumed silica such as “Aerosil” (manufactured by Nippon Aerosil). In addition, silica gel such as “Snowtex PS” (manufactured by Nissan Chemical Industries) is used as the chain silica, and commercially available silica gel such as “Adelite AT-20A” (manufactured by Asahi Denka Kogyo Co., Ltd.) is used as the aluminum-modified silica. Can do.

  The water-dispersible silica is preferably contained in the metal surface treatment agent at a solid content of 0.05 to 100 g / L, particularly 0.5 to 60 g / L. If the content of the water-dispersible silica is less than 0.05 g / L, the effect of improving the corrosion resistance may be insufficient. If the content exceeds 100 g / L, the effect of improving the corrosion resistance is not seen. May decrease.

  The metal surface treating agent of the present invention may contain a zirconium compound and / or a titanium compound as an additional component. Examples of the zirconium compound include zirconyl ammonium carbonate, zircon hydrofluoric acid, zircon ammonium fluoride, potassium zircon fluoride, sodium zircon fluoride, zirconium acetylacetonate, zirconium butoxide 1-butanol solution, zirconium n-propoxide and the like. Examples of titanium compounds include titanium hydrofluoric acid, titanium ammonium fluoride, potassium potassium oxalate, titanium isopropoxide, isopropyl titanate, titanium ethoxide, titanium-2-ethyl-1-hexanolate, and tetraisopropyl titanate. , Tetra n-butyl titanate, potassium potassium fluoride, sodium titanium fluoride and the like. The said compound may be used individually by 1 type, and may use 2 or more types together.

  The zirconium compound and / or the titanium compound are contained in the metal surface treatment agent at a concentration of 0.01 to 50 g / L, particularly 0.05 to 5 g / L, respectively, as the amount of zirconium ions or titanium ions. It is preferable. When the content of each of the above compounds is less than 0.01 g / L, the corrosion resistance may be insufficient. When the content exceeds 50 g / L, the effect of improving the work adhesion performance is not observed, and the bath stability is decreased. There is a case.

  The metal surface treating agent of the present invention may contain a thiocarbonyl group-containing compound as an additional component. Thiocarbonyl compounds include thiourea, dimethylthiourea, 1,3-dimethylthiourea, dipropylthiourea, dibutylthiourea, 1,3-diphenyl-2-thiourea, 2,2-ditolylthiourea, thioacetamide, sodium dimethyldithiocarbamate Tetramethylthiuram monosulfide, tetrabutylthiuram disulfide, zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate, pentamethylenedithiocarbamate piperidine salt, zinc diethyldithiocarbamate, sodium diethyldithiocarbamate, zinc isopropylxanthate, Less thiocarbonyl groups such as ethylenethiourea, dimethylxanthogen sulfide, dithiooxamide, polydithiocarbamic acid or its salts Compounds can be exemplified also contain one. The said compound may be used independently and may use 2 or more types together.

  The thiocarbonyl group-containing compound is preferably contained in the metal surface treatment agent of the present invention at a concentration of 0.01 to 100 g / L, particularly 0.1 to 10 g / L. If the content of the above compound is less than 0.01 g / L, the effect of improving corrosion resistance may be insufficient, and if it exceeds 100 g / L, the effect of improving corrosion resistance may be saturated and uneconomical.

  The metal surface treating agent of the present invention may contain a water-soluble acrylic resin as an additional component. The water-soluble acrylic resin is a copolymer mainly composed of acrylic acid and / or methacrylic acid, and examples thereof include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, derivatives thereof, and others Copolymers with other acrylic monomers can also be used. In particular, the acrylic acid and / or methacrylic acid monomer ratio in the copolymer is preferably 70% or more.

  Moreover, it is preferable that the molecular weight of an acrylic resin is 10,000 or more on a weight average. More preferably, it is 300,000 to 2,000,000. If it exceeds 2 million, the viscosity increases and the efficiency of handling work may decrease. If it is less than 10,000, the said improvement effect may not fully be exhibited.

  The acrylic resin is preferably contained in the metal surface treatment agent at a concentration of 0.1 to 100 g / L, particularly 5 to 80 g / L. If the concentration of the acrylic resin is less than 0.1 g / L, the effect of improving the folding adhesion and the deep drawing property may be insufficient. If the concentration exceeds 100 g / L, the bending adhesion and the deep drawing improving effect are saturated. , It may be uneconomical.

The metal surface treating agent of the present invention can further improve the corrosion resistance by adding phosphate ions. This addition of phosphate ions can be performed by adding a compound capable of forming phosphate ions in water. Examples of such compounds include phosphoric acid, phosphates such as Na ₃ PO ₄ , Na ₂ HPO ₄ , and NaH ₂ PO ₄ , condensed phosphoric acid such as condensed phosphoric acid, polyphosphoric acid, metaphosphoric acid, and diphosphoric acid, or Those salts are mentioned. These may be used alone or in combination of two or more.

  The addition amount of the phosphate ion is preferably 0.01 to 100 g / L, more preferably 0.1 to 10 g / L in the metal surface treatment agent. If the amount added is less than 0.01 g / L, the effect of improving the corrosion resistance may be insufficient. If the amount added exceeds 100 g / L, the zinc-plated steel material is excessively etched, resulting in performance degradation or other components. When an aqueous resin is included, gelation may be caused.

  Further, the metal surface treating agent of the present invention may further contain other components. For example, tannic acid or a salt thereof, phytic acid or a salt thereof, and an aqueous resin can be exemplified, for example, urethane resin, epoxy resin, ethylene acrylic copolymer, phenol resin, polyester resin, polyolefin resin, alkyd resin. Polycarbonate resin or the like can be used. These resins may be used alone, in combination of two or more kinds, or further copolymerized and used. Moreover, when using resin, in order to improve the film forming property and form a more uniform and smooth coating film, an organic solvent may be used. Furthermore, a leveling agent, a wettability improver, and an antifoaming agent may be used.

  The metal surface treatment agent of the present invention includes cold rolled steel, hot rolled steel, stainless steel, electrogalvanized steel, hot dip galvanized steel, zinc-aluminum alloy plated steel, zinc-iron alloy plated steel, zinc-magnesium. Alloy-based plated steel materials, zinc-aluminum-magnesium alloy-based plated steel materials, aluminum-based plated steel materials, aluminum-silicon alloy-based plated steel materials, tin-based plated steel materials, lead-tin alloy-based plated steel materials, chromium-based plated steel materials, nickel-based plated steel materials Although it is used as a surface treatment agent for metal steel materials such as, it is particularly effective for metal-coated steel materials (plated steel materials).

  As a method for using this surface treatment agent, that is, as a surface treatment method, the metal surface treatment agent may be applied to an object to be coated, and the object to be coated may be dried after the application. Then, the method of applying the metal surface treatment agent of the present invention and drying using residual heat may be used.

In any case, the drying conditions can be from room temperature to 250 ° C. for 2 seconds to 1 hour. If it exceeds 250 ° C., performance deterioration such as adhesion and corrosion resistance may occur. Preferably, it is dried at 40 to 180 ° C. for 5 seconds to 20 minutes. In the surface treatment method, the coating amount of the metal surface treatment agent of the present invention is preferably a film mass of 0.1 mg / m ² or more. When the film mass is less than 0.1 mg / m ² , the rust prevention property may be insufficient. On the other hand, a and the adhesion amount is too much uneconomic as painting pretreatment agent, more preferably from 0.5 to 500 mg / m ^2, more preferably from 1-250 mg / m ^2.

  In the above surface treatment method, the method for applying the metal surface treatment agent is not particularly limited, and it can be applied by commonly used roll coating, shower coating, spraying, dipping, brush coating, or the like. Moreover, the steel material used as the object to be processed is the above-described metal steel material, and is particularly suitable for the treatment of various plated steel materials.

  The method for producing a coated steel material according to the present invention is a method in which the metal steel material is surface-treated with the metal surface treatment agent, dried, and then coated with an upper film layer. Examples of the coating layer include a coating system in which a top coat is further applied after applying and drying a non-chromate primer, and a functional coating having functions such as fingerprint resistance and lubricity. The above manufacturing method can be applied not only to pre-coated steel materials but also to post-coated steel materials. In the present invention, the coated steel materials include these. In the present invention, the steel material is a concept including a steel plate.

As the non-chromate primer that can be used in the present invention, any primer that does not use a chromate rust preventive pigment during blending of the primer can be used. As such a primer, a primer (V / P pigment primer) using a vanadic acid type anticorrosive pigment and a phosphoric acid type anticorrosive pigment or a primer using a calcium silicate type anticorrosive pigment is preferable.
The applied film thickness of the primer is preferably 1 to 20 μm in terms of dry film thickness. If it is less than 1 μm, the corrosion resistance may be insufficient, and if it exceeds 20 μm, the work adhesion may be lowered.
The baking and drying conditions for the non-chromate primer can be, for example, a metal surface temperature of 150 to 250 ° C. and a time of 10 seconds to 5 minutes.

  The top coat is not particularly limited, and all usual top coats for painting can be used. Further, the functional coating is not particularly limited, and all coatings currently applied on the chromate pretreatment film can be used. The method for applying the non-chromate primer, top coat, and functional coating is not particularly limited, and commonly used roll coat, shower coat, air spray, airless spray, immersion, and the like can be used.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples. In the examples, pH and viscosity were measured at 25 ° C. In the examples, GC is an abbreviation for gas chromatography, and NMR is an abbreviation for nuclear magnetic resonance spectroscopy. The average molecular weight is a GPC polystyrene equivalent weight average molecular weight, and the viscosity is based on measurement with a B-type rotational viscometer (25 ° C.).

[Synthesis Example 1]
A 15% by weight aqueous solution of polyallylamine (manufactured by Nitto Boseki Co., Ltd., PAA-01 type, average molecular weight 1000) is removed by removing water under reduced pressure, and methanol is added to perform solvent exchange. It was. In this, 77.9 mass parts (0.33 mol) of 3-glycidoxypropyl trimethoxysilane was added, and it stirred at 60 to 70 degreeC for 5 hours. As the reaction proceeds, the raw material 3-glycidoxypropyltrimethoxysilane is consumed. Therefore, when this solution was measured by gas chromatography, the peak of the starting material 3-glycidoxypropyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 3-glycidoxypropyltrimethoxysilane, and a signal that was newly derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and the solution was diluted with methanol to adjust the active ingredient to 15% by mass to obtain a primer composition. This composition is a yellow transparent solution that is rapidly mixed with water, has a pH of 11.7, a viscosity of 2.7 mPa · s, a degree of polymerization of the base polymer portion of about 17, and an average structural formula shown below. there were.

[Synthesis Example 2]
Water was removed from 500.0 parts by mass of a 20% by mass polyallylamine aqueous solution [average molecular weight 2500] under reduced pressure, methanol was added to perform solvent exchange, and a 15% by mass methanol solution was obtained. In this, 101.5 mass parts (0.43 mol) of 3-glycidoxypropyl trimethoxysilane was added, and it stirred at 60 to 70 degreeC for 5 hours. As the reaction proceeds, the raw material 3-glycidoxypropyltrimethoxysilane is consumed. Therefore, when this solution was measured by gas chromatography, the peak of the starting material 3-glycidoxypropyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 3-glycidoxypropyltrimethoxysilane, and a signal that was newly derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and the solution was diluted with methanol to adjust the active ingredient to 15% by mass to obtain a primer composition. This composition is a yellow transparent solution that is rapidly mixed with water, has a pH of 11.6, a viscosity of 15.1 mPa · s, a degree of polymerization of the base polymer portion of about 44, and an average structural formula shown below. there were.

[Synthesis Example 3]
Water was removed from 500.0 parts by mass of a 20% by mass polyallylamine aqueous solution (average molecular weight 700) under reduced pressure, methanol was added to perform solvent exchange, and a 15% by mass methanol solution was obtained. 99.1 parts by mass (0.42 mol) of 3-glycidoxypropyltrimethoxysilane was added thereto, and the mixture was stirred at 60 ° C. to 70 ° C. for 5 hours. As the reaction proceeds, the raw material 3-glycidoxypropyltrimethoxysilane is consumed. Therefore, when this solution was measured by gas chromatography, the peak of the starting material 3-glycidoxypropyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 3-glycidoxypropyltrimethoxysilane, and a signal that was newly derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and the solution was diluted with methanol to adjust the active ingredient to 15% by mass to obtain a primer composition. This composition is a yellow transparent solution that is rapidly mixed with water, has a pH of 11.8, a viscosity of 1.9 mPa · s, a degree of polymerization of the base polymer portion of about 12, and an average structural formula shown below. there were.

[Synthesis Example 4]
A 15% by weight aqueous solution of polyallylamine (manufactured by Nitto Boseki Co., Ltd., PAA-01 type, average molecular weight 1000) is removed by removing water under reduced pressure, and methanol is added to perform solvent exchange. It was. To this, 81.2 parts by mass (0.33 mol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added and stirred at 60 ° C. to 70 ° C. for 5 hours. As the reaction proceeds, the raw material 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is consumed. Therefore, when this solution was measured by gas chromatography, the peak of the raw material 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and a new signal that was thought to be derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and the solution was diluted with methanol to adjust the active ingredient to 15% by mass to obtain a primer composition. This composition is a yellow transparent solution that is rapidly mixed with water, has a pH of 11.5, a viscosity of 3.5 mPa · s, a polymerization degree of the base polymer portion of about 17, and an average structural formula shown below. there were.

[Synthesis Example 5]
A 15% by weight aqueous solution of polyallylamine (manufactured by Nitto Boseki Co., Ltd., PAA-01 type, average molecular weight 1000) is removed by removing water under reduced pressure, and methanol is added to perform solvent exchange. It was. In this, 77.2 mass parts (0.33 mol) of 3-acryloxypropyltrimethoxysilane was added, and it stirred at 60 to 70 degreeC for 5 hours. As the reaction proceeds, the raw material 3-acryloxypropyltrimethoxysilane is consumed. Therefore, when this solution was measured by gas chromatography, the peak of the starting material 3-acryloxypropyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 3-acryloxypropyltrimethoxysilane, and a new signal derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and the solution was diluted with methanol to adjust the active ingredient to 15% by mass. This solution is a yellow transparent solution that is rapidly mixed with water, has a pH of 11.7, a viscosity of 2.7 mPa · s, a degree of polymerization of the base polymer portion of about 17, and an average structural formula shown below. there were.

[Synthesis Example 6]
A 15% by weight aqueous solution of polyallylamine (manufactured by Nitto Boseki Co., Ltd., PAA-01 type, average molecular weight 1000) is removed by removing water under reduced pressure, and methanol is added to perform solvent exchange. It was. To this was added 65.5 parts by mass (0.33 mol) of 3-chloropropyltrimethoxysilane, and the mixture was stirred at 60 ° C. to 70 ° C. for 40 hours. The chloride ion content in the reaction solution is increased by the hydrochloric acid generated as the reaction proceeds. Therefore, when the chloro ion content of this solution was measured by potentiometric titration using silver nitrate, the chloro ion content in the solution was 2.0% by mass, which was the same as the chloro ion content generated when the reaction was completed. The amount was confirmed to be complete. Moreover, when this solution was measured by gas chromatography, the peak of the raw material 3-chloropropyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 3-chloropropyltrimethoxysilane, and a signal that was thought to be newly derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and 17.82 parts by mass (0.33 mol) of sodium methylate was further added to this solution, followed by stirring at 60 ° C. to 70 ° C. for 1 hour, and amine hydrochloride in the solution. Was converted to sodium chloride. Thereafter, the precipitated sodium chloride was filtered and diluted with methanol to adjust the active ingredient to 15% by mass. This solution is a yellow transparent solution that quickly mixes with water, has a pH of 12.2, a viscosity of 8.6 mPa · s, contains 0.5% by mass of sodium chloride-derived chloro ions, The degree of polymerization was about 17, and the average structural formula was as shown below.

[Synthesis Example 7]
A 15% by weight aqueous solution of polyallylamine (manufactured by Nitto Boseki Co., Ltd., PAA-01 type, average molecular weight 1000) is removed by removing water under reduced pressure, and methanol is added to perform solvent exchange. It was. In this, 32.8 mass parts (0.17 mol) of 3-chloropropyl trimethoxysilane was added, and it stirred at 60 degreeC-70 degreeC for 40 hours. The chloride ion content in the reaction solution is increased by the hydrochloric acid generated as the reaction proceeds. Therefore, when the chloro ion content of this solution was measured by potentiometric titration using silver nitrate, the chloro ion content in the solution was 1.0% by mass, which was the same as the chloro ion content generated when the reaction was completed. The amount was confirmed to be complete. Moreover, when this solution was measured by gas chromatography, the peak of the raw material 3-chloropropyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 3-chloropropyltrimethoxysilane, and a signal that was thought to be newly derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and 8.9 parts by mass (0.17 mol) of sodium methylate was further added to this solution, followed by stirring at 60 ° C. to 70 ° C. for 1 hour, and amine hydrochloride in the solution. Was converted to sodium chloride. Thereafter, the precipitated sodium chloride was filtered and diluted with methanol to adjust the active ingredient to 15% by mass. This solution is a yellow transparent solution that is rapidly mixed with water, has a pH of 12.3, a viscosity of 2.1 mPa · s, contains 0.4% by mass of sodium chloride-derived chloro ions, The degree of polymerization was about 17, and the average structural formula was as shown below.

[Synthesis Example 8]
Polyethyleneimine (average molecular weight 1000) 75.0 parts by mass was dissolved in methanol to obtain a 15% by mass methanol solution. In this, 77.9 mass parts (0.33 mol) of 3-glycidoxypropyl trimethoxysilane was added, and it stirred at 60 to 70 degreeC for 5 hours. As the reaction proceeds, the raw material 3-glycidoxypropyltrimethoxysilane is consumed. Therefore, when this solution was measured by gas chromatography, the peak of the starting material 3-glycidoxypropyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 3-glycidoxypropyltrimethoxysilane, and a signal that was newly derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and the solution was diluted with methanol to adjust the active ingredient to 15% by mass to obtain a primer composition. This composition is a yellow transparent solution that is rapidly mixed with water, has a pH of 11.1, a viscosity of 2.1 mPa · s, a degree of polymerization of the base polymer portion of about 23, and an average structural formula shown below. there were.

[Synthesis Example 9]
Polyethyleneimine (average molecular weight 1000) 75.0 parts by mass was dissolved in methanol to obtain a 15% by mass methanol solution. In this, 77.9 mass parts (0.33 mol) of 3-acryloxypropyltrimethoxysilane was added, and it stirred at 60 to 70 degreeC for 5 hours. As the reaction proceeds, the raw material 3-acryloxypropyltrimethoxysilane is consumed. Therefore, when this solution was measured by gas chromatography, the peak of the starting material 3-acryloxycypropyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 3-acryloxypropyltrimethoxysilane, and a new signal derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and the solution was diluted with methanol to adjust the active ingredient to 15% by mass to obtain a primer composition. This composition is a yellow transparent solution that is rapidly mixed with water, has a pH of 10.9, a viscosity of 1.8 mPa · s, a degree of polymerization of the base polymer portion of about 23, and an average structural formula shown below. there were.

[Synthesis Example 10]
Polyethyleneimine (average molecular weight 1000) 75.0 parts by mass was dissolved in methanol to obtain a 15% by mass methanol solution. To this was added 65.5 parts by mass (0.33 mol) of 3-chloropropyltrimethoxysilane, and the mixture was stirred at 60 ° C. to 70 ° C. for 40 hours. The chloride ion content in the reaction solution is increased by the hydrochloric acid generated as the reaction proceeds. Therefore, when the chloro ion content of this solution was measured by potentiometric titration using silver nitrate, the chloro ion content in the solution was 2.0% by mass, which was the same as the chloro ion content generated when the reaction was completed. The amount was confirmed to be complete. Moreover, when this solution was measured by gas chromatography, the peak of the raw material 3-chloropropyltrimethoxysilane was not detected. Moreover, when NMR of silicon was measured, there was no signal of 3-chloropropyltrimethoxysilane, and a signal that was thought to be newly derived from the target compound was confirmed. From the above, it was judged that the reaction was completed, and 17.82 parts by mass (0.33 mol) of sodium methylate was further added to this solution, followed by stirring at 60 ° C. to 70 ° C. for 1 hour, and amine hydrochloride in the solution. Was converted to sodium chloride. Thereafter, the precipitated sodium chloride was filtered and diluted with methanol to adjust the active ingredient to 15% by mass. This solution is a yellow transparent solution that quickly mixes with water, has a pH of 11.2, a viscosity of 5.6 mPa · s, contains 0.1% by mass of sodium chloride-derived chloro ions, The degree of polymerization was about 23, and the average structural formula was as shown below.

[ Reference Example 1]
10 g of the polymer compound obtained in Synthesis Example 1 as a non-volatile component was added to 1 liter of pure water and stirred for 5 minutes at room temperature to obtain a metal surface treating agent. A bar coater No. was applied to a commercially available hot-dip galvanized steel sheet (manufactured by Nippon Test Panel Co., Ltd .; 70 × 150 × 0.4 mm) obtained by degreasing and drying the obtained metal surface treatment agent. 20 and dried at a metal surface temperature of 105 ° C. for 10 minutes. After that, a V / P pigment-containing non-chromate primer was added to the bar coater no. 16 was applied so that the dry film thickness was 5 μm, and dried at a metal surface temperature of 215 ° C. for 5 minutes. Furthermore, as a top coat, Flexcoat 1060 (polyester-based top coat; manufactured by Nippon Paint Co., Ltd.) was used as a bar coater no. The coating was applied at 36 so that the dry film thickness was 15 μm, and the metal surface temperature was dried at 230 ° C. to obtain a test plate. The obtained test plates were evaluated for bending adhesion and corrosion resistance according to the following evaluation methods, and the results are shown in Table 1.

[Examples 1 to 10, Reference Examples 2 to 5 , Comparative Examples 1 to 3]
As shown in Table 1, the compounds obtained in the synthesis examples, the types and concentrations of silane compounds, water-dispersible silica, zirconium ions, thiocarbonyl group-containing compounds, water-soluble acrylic resins, and phosphate ions A metal surface treating agent was prepared in the same manner as in Reference Example 1 except that it was changed. Using these metal surface treatment agents, test plates were prepared in the same manner as in Reference Example 1 and evaluated. The results obtained are listed in Table 1.

[Comparative Example 4]
Instead of the metal surface treatment agent, a commercially available coating type chromate treatment agent (resin-containing type) was applied and dried so that the chromium adhesion amount was 20 mg / m ² , and a chromium-containing primer (strontium chromate pigment-containing primer) A test plate was prepared and evaluated in the same manner as in Example 1 except that was used, and the results obtained are shown in Table 1.

[Examples 11 to 13 and Comparative Example 5]
A treated plate was prepared in the same manner as in Reference Example 1, and a fingerprint-resistant coating (fluorinated alkyl-based thermoplastic resin) was used as a functional coating instead of the primer and top coat. 5 was applied so that the dry film thickness was 1 μm, and dried at a metal surface temperature of 120 ° C. to prepare a test plate. The evaluation results of these test plates are shown in Table 2.

[Examples 14 to 16 , Comparative Example 6]
A treated plate was prepared in the same manner as in Reference Example 1, and a lubricating coating (polyether-based thermosetting resin) was used as a functional coating instead of the primer and the top coat. 5 was applied so that the dry film thickness was 1 μm, and dried at a metal surface temperature of 120 ° C. to prepare a test plate. The evaluation results of these test plates are shown in Table 2.

[Comparative Example 7]
Instead of a metal surface treatment agent, a commercially available coating-type chromate treatment agent (resin-containing type) was applied and dried so that the chromium adhesion amount was 20 mg / m ² , and a chromium-containing primer (strontium chromate pigment-containing primer) Test plates were prepared and evaluated in the same manner as in Examples 11 and 14 except that they were used. The results obtained are shown in Table 2.

  The silane compounds, water-dispersible silica, compounds that form zirconium ions, thiocarbonyl group-containing compounds, water-soluble acrylic resins, and compounds that form phosphate ions used in Tables 1 and 2 are the following commercially available products: It is.

[Silane compounds]
Synthesis Examples 1 to 10: Polymer compounds described in Synthesis Examples 1 to 1: KBM-903 (γ-aminopropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.)
[Water-dispersible silica]
Snowtex N (manufactured by Nissan Chemical Industries)
[Compounds that form zirconium ions]
Zirconazole AC-7 (Zirconyl ammonium carbonate; manufactured by Daiichi Rare Element Co., Ltd.)
[Thiocarbonyl group-containing compound]
Thiourea (reagent)
[Water-soluble acrylic resin]
Polyacrylic acid (reagent) weight average molecular weight 1 million [compound that forms phosphate ion]
Phosphoric acid (reagent)

[Evaluation method]
Evaluation of bending adhesion, deep drawability, corrosion resistance (1) in Examples 1 to 10, Reference Examples 1 to 5 and Comparative Examples 1 to 4, and paint adhesion in Examples 11 to 16 and Comparative Examples 5 to 7 Evaluation of property, corrosion resistance (2), fingerprint resistance, and lubricity was performed based on the following methods and evaluation criteria.

Bending adhesion Under a 20 ° C environment, the test plate is bent at 180 ° C using a conical mandrel tester with a 2mmφ spacer in between. And evaluated according to the following criteria.
A: No crack B: Crack in front of the processed part C: Peeling area is less than 20% of the processed part D: Peeling area is not less than 20% of the processed part and less than 80% E: Peeling area is not less than 80% of the processed part

A cylindrical drawing test was conducted under the conditions of drawing ratio of 2.3 ° C., wrinkle suppression pressure: 2 t, punch R: 5 mm, die shoulder R: 5 mm, oil-free under an environment of deep drawability of 20 ° C. Then, the peeling width of the coating film was measured from the cross cut part and evaluated according to the following criteria.
A: Blowing width is less than 1 mm B: Blowing width is 1 mm or more and less than 2 mm C: Blowing width is 2 mm or more and less than 3 mm D: Blowing width is 3 mm or more and less than 5 mm E: Blowing width is 5 mm or more

Corrosion resistance (1)
(Cut part)
A cross-cut was put into the test plate, and a salt spray test based on JIS Z 2371 was conducted for 500 hours, and then the blister width on one side of the cut part was measured and evaluated according to the following criteria.
A: The blister width is 0mm
B: Blowing width is less than 1 mm C: Blowing width is 1 mm or more and less than 3 mm D: Blowing width is 3 mm or more and less than 5 mm E: Blowing width is 5 mm or more (end face)
After a salt spray test based on JIS Z 2371 was performed for 500 hours on the test plate, the blister width from the upper burr end face was evaluated on the same basis as the cut part.

Paint adhesion To the pre-coated steel sheets produced in Examples and Comparative Examples, a melamine alkyd resin paint (Amirac No. 1000, manufactured by Kansai Paint Co., Ltd.) was further applied to a dry film thickness of 30 μm using a bar coater. And baked at a furnace temperature of 130 ° C. for 20 minutes. Next, after leaving overnight, 7 mm Erichsen processing was performed. Adhesive tape was applied to the processed part, and the tape was immediately pulled in an oblique 45 ° direction to be peeled off, and the following evaluation was performed based on the peeled area ratio.
A: No peeling B: Peeling area ratio less than 5% C: Peeling area ratio 5% or more, less than 30% D: Peeling area ratio 30% or more, less than 50% E: Peeling area ratio 50% or more

Corrosion resistance (2)
(Flat part)
According to the salt spray test method described in JIS Z 2371, the precoated steel sheets produced in the examples and comparative examples were sprayed with 5% saline on the test plate at an ambient temperature of 35 ° C., and white rust after 240 hours. The following evaluation was performed according to the incidence.
A: No white rust occurrence B: White rust occurrence rate less than 10% C: White rust occurrence rate 10% or more, less than 20% D: White rust occurrence rate 20% or more, less than 30% E: White rust occurrence rate 30% or more (process section)
The pre-coated steel plates produced in the examples and comparative examples were subjected to 7 mm Erichsen processing, and 5% saline was sprayed onto the test plates at an ambient temperature of 35 ° C. according to the salt spray test method described in JIS Z 2371. Evaluation was performed based on the same standard as that of the flat portion by the white rust occurrence rate in the processed portion after 72 hours.

Fingerprint resistance Examples 11 to 13 and fingerprints were attached to the coatings of the precoated steel sheets produced in Comparative Examples 5 and 7, and the visibility of the fingerprint was visually determined to evaluate the following.
A: The fingerprint trace is not visible B: The fingerprint trace is very slightly visible C: The fingerprint trace is visible D: The fingerprint trace is conspicuous E: The fingerprint trace is very conspicuous

Lubricity Examples 14 to 16 and the precoated steel sheets produced in Comparative Examples 6 and 7 were subjected to a molding test at room temperature under the following conditions using a cylindrical punch hydraulic forming tester, and the mold galling property was an index of lubricity. As evaluated.
Punch diameter: 70mmφ
Blank diameter: 150mm
Pressing load: 5 kgf / cm ²
Molding speed: 3.3 × 10 ⁻² m / s
Tool condition: FCD-500
In addition, all were shape | molded to 80% of the maximum shaping | molding height. The mold galling property was visually determined and evaluated as follows.
A: Formable, no defects on the surface of the steel sheet B: Formable, no defects on the surface of the steel sheet, slight discoloration of the sliding surface C: Formable, slight galling on the surface of the steel sheet D: Formable, steel sheet Many slight galling traces are generated on the surface E: Molding is impossible

  The results of the above Examples and Comparative Examples demonstrate that the primer composition of the present invention gives good results for adhesion.

Claims (10)

Under following general formula (1)

(In the formula, m is 10 ≦ m ≦ 260, n is 1 ≦ n ≦ 100, 0.003 ≦ n / (m + n) ≦ 0.9, and R ¹ is a hydrogen atom having 1 to 4 carbon atoms. An alkyl group or an acetyl group, a and b are integers of 1 to 3, X is an optionally substituted alkylene group having 1 to 10 carbon atoms, and the substituent is 1 to 6 carbon atoms. an alkyl group, Y is a direct bond, an oxygen atom or a CHR ⁵ group, represents an R ^2, R ^3, R ⁴ and R ⁵ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ³ or R ⁴ and R ⁵ may combine to form a saturated carbocycle.)
A silicon-containing water-soluble polymer compound having a plurality of primary amino groups and hydrolyzable silyl groups and / or silanol groups, having a repeating unit represented by the following general formula (2)

(In the formula, m is 10 ≦ m ≦ 260, n is 1 ≦ n ≦ 100, 0.003 ≦ n / (m + n) ≦ 0.9, and X is the carbon number that may have a substituent. 1 to 10 alkylene group, the substituent is an alkyl group having 1 to 6 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group, and R ′ is a hydrogen atom or A methyl group, and a is an integer of 1 to 3.)
A silicon-containing water-soluble polymer compound having a plurality of primary amino groups and a hydrolyzable silyl group and / or silanol group, and the following general formula (3):

(In the formula, m is 10 ≦ m ≦ 260, n is 1 ≦ n ≦ 100, 0.003 ≦ n / (m + n) ≦ 0.9, and X is the carbon number that may have a substituent. 1 to 10 alkylene group, the substituent is an alkyl group having 1 to 6 carbon atoms, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acetyl group, and a is 1 to 3 (It is an integer.)
The weight average molecular weight selected from the group consisting of silicon-containing water-soluble polymer compounds having a plurality of primary amino groups and hydrolyzable silyl groups and / or silanol groups, having a repeating unit represented by the formula: And / or (part) hydrolysis condensate thereof is dissolved in water and / or an organic solvent so that the metal surface treatment agent contains 0.01 to 200 g / L. further, in the metal surface treatment agent, characterized and to Rukin genus surface treatment agent in that it comprises 0.05 to 100 g / L of water-dispersible silica solids. Furthermore, in the metal surface treatment agent, metal according to claim 1, wherein the zirconium compound 0.01 to 50 g / L and / or titanium compound as zirconium ions, characterized in that it comprises 0.01 to 50 g / L as titanium ions Surface treatment agent. Furthermore, in the metal surface treatment agent of claim 1 or 2, wherein the thiocarbonyl group-containing compound comprising 0.01 to 100 g / L and / or a water-soluble acrylic resin 0.1 to 100 g / L Metal surface treatment agent. Furthermore, 0.01-100 g / L of phosphate ions are contained in the metal surface treatment agent, the metal surface treatment agent according to any one of claims 1 to 3 . A metal surface treatment method for a steel material, wherein the surface treatment is performed with the metal surface treatment agent according to any one of claims 1 to 4 . The metal surface treatment method according to claim 5 , wherein the steel material is a metal-coated steel material. A surface-treated steel material obtained by the method according to claim 5 or 6 . A method for producing a coated steel material, further comprising providing an upper coating layer after treating the steel material with the metal surface treatment agent according to any one of claims 1 to 4 . The method for producing a coated steel material according to claim 8 , wherein the steel material is a metal-coated steel material. A coated steel material obtained by the method according to claim 8 or 9 .